KR20170091065A - Polyamide alloy high heat resistant resin composition and electronic product - Google Patents

Abstract

The present invention relates to a highly heat-resistant polyamide alloy resin composition, and an electrical/electronic component. According to the present invention, provided is a highly heat-resistant polyamide alloy resin composition obtained by adding an impact reinforcement agent-combined compatibilizer into an alloy material consisting of a polyamide resin and a syndiotactic polystyrene resin. Moreover, provided is an electrical/electronic component exhibiting high heat resistance and mechanical properties by using the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyamide alloy heat-resistant resin composition,

The present invention relates to a polyamide alloy high heat-resistant resin composition and electric and electronic components, and more particularly, to a polyamide resin and a syndiotactic polystyrene resin composition which are blended with a compatibilizing agent serving both as an impact modifier and an improved mechanical property Heat resistant resin composition capable of imparting high heat resistance, and electric and electronic parts made of the composition.

Polyamide resin, which is a kind of engineering plastics, has excellent mechanical strength, abrasion resistance, heat resistance, chemical resistance, electrical insulation and arc resistance and is used in a wide range of applications such as automobile, electric and electronic parts and industrial materials.

Many techniques for alloying syndiotactic polystyrenes having superior heat resistance to the polyamide resin have been proposed. Since these polymer blends have no or low compatibility with each other, a compatibilizer is usually used for the purpose of enhancing compatibility . However, when a certain type of compatibilizing agent is added, or when a compatibilizing agent is used in an excess amount more than necessary, the mechanical properties and thermal properties are deteriorated.

For example, when a styrene-based rubber is used as a compatibilizing agent, compatibility and tensile and thermal properties may be reduced along with increased impact and bending properties. When polyphenylene oxide-based commercialization is used, But the impact, bending and thermal properties of the two kinds of compatibilizers are increased. However, these two kinds of compatibilizers each show a limitation in improving mechanical properties and thermal properties when they are added in an excess amount. There arises a problem that the compatibilizer remaining between the matrix and the domain reacts to reduce the area of the matrix to reduce the thermal properties as well as the mechanical properties (US Pat. No. 6,093,768).

In order to solve the problems of the prior art as described above, the present invention provides a polyamide alloy high heat-resistant resin composition for high heat-resistance electrical and electronic components, which comprises a compatibilizing agent for both an impact modifier and a synergistic effect of mechanical properties and thermal properties And an electric and electronic component therefrom.

In order to achieve the above object, the present invention provides a filler filled polyamide and syndiotactic polystyrene alloy, wherein the syndiotactic polystyrene is contained in a range of 17 to 30 wt% of 100 wt% of the alloy composition, A compatibilizing agent serving as both an impact modifier and a styrene-based rubber in which the functional group for amide bonding and the styrene-based rubber are connected in a graft structure is contained in an amount of 0.5 to 7 wt% of 100 wt% of the alloy composition, and the filler is a glass fiber having an aspect ratio of 0.31 or more A polyamide alloy and a heat resistant resin composition.

Further, the present invention provides an electric / electronic part which is molded from the polyamide alloy high heat-resistant resin composition and has a heat distortion temperature (HDT) of 244 to 253 占 폚.

According to the present invention, there is provided an alloy and heat-resistant resin composition of a polyamide resin and a syndiotactic polystyrene combined with a compatibilizing agent serving as both an impact modifier and an electric and electronic component having mechanical properties and high heat resistance characteristics .

Hereinafter, the present invention will be described in detail.

The polyamide alloy high heat-resistant resin composition of the present invention is a filler-filled polyamide and syndiotactic polystyrene alloy, wherein the syndiotactic polystyrene is contained in a range of 17 to 30 weight% of 100 weight% of the alloy composition, A compatibilizing agent serving both as a polyamide linkage functional group and a styrene-based rubber in a graft structure is contained in an amount of 0.5 to 7 wt% of 100 wt% of the alloy composition, and the filler is a glass fiber having an aspect ratio of 0.31 or more .

The functional group for polyamide bonding may be, for example, a functional group derived from a compound selected from at least one of maleic anhydride and glycidyl (meth) acrylate.

The styrene-based rubber is directly bonded to the syndiotactic polystyrene resin in the above-mentioned alloy composition, and examples thereof include styrene-butylene-styrene rubber, styrene-isoprene-styrene rubber, styrene- -Propylene-styrene rubber, and styrene-ethylene-butylene-styrene rubber.

For example, the compatibilizing agent serving as the impact modifier may be contained in the range of 0.5 to 7 wt%, or 1 to 5.1 wt% in the alloy composition. In this range, impact reinforcement and compatibility can be maximized, The effect of improving the thermal deformation temperature and the spiral characteristics can be provided.

The polyamide has, for example, a relative viscosity of 2.3 to 2.8, or 2.3 to 2.5 as measured in a 96% sulfuric acid solvent, and is suitable to constitute syndorotactic polystyrenes and alloys within this range .

The polyamide may be included, for example, in the range of 39 to 45 weight percent of the alloy composition, and may be optimized to constitute syndiotactic polystyrene and allyl within this range.

As the polyamide resin, for example, a lactam having a cyclic structure or a polycondensate of two or more kinds of w-amino acids can be used, and diacids and diamines can be used. Further, homopolyamides, Polyamide type.

The polyamide resin is at least one selected from the group consisting of polyamide 6,6, polyamide 12, polyamide 6,10, polyamide 6,12, polyphthalamide, and polyamide 4,6. It may be preferable to use 90 to 40% by weight of a polyamide second resin selected from at least one selected from the group consisting of polycaprolactam (nylon 6) and polylauroractam (nylon 12) in view of complementary physical properties.

The syndiotactic polystyrenes have a weight average molecular weight (Mw) of 130,000 to 200,000 g / mol, or 150,000 to 200,000 g / mol, a melt index (300 ° C, 1.2kg) of 5-30 g / 10 minutes, or 5-15 g / 10 minutes is suitable for constituting polyamide and alloy.

As a specific example, the filler may be a glass fiber having an aspect ratio (L / D) of 0.31 or more to less than 5.

As another example, the glass fiber may have an aspect ratio (L / D) of length (length L of glass fiber) / cross section (cross section D of glass fiber) of not less than 0.31 and not more than 1, Polymers in polystyrene and polyamide resin compositions can maintain a very strong bonding force to increase rigidity, and thus can play a role of replacing resins and metals, which are expensive in processing plastic parts such as automobiles, where stiffness is given priority.

The cross section D corresponds to the longest side of the cross section when the cross section cut perpendicular to the longitudinal direction of the glass fiber is a rectangle, and the longest cross section when the cross section is elliptic cross section.

As a specific example, the glass fibers may have a length of 1 to 5 mm, or 2 to 3 mm, a diameter of 10 to 20 μm, 10 to 15 μm, or 10 to 13 μm.

The glass fiber may be one surface-treated with aminosilane as elliptical glass fiber, for example.

As another example, the glass fiber may have a rectangular or elliptical cross section cut perpendicular to the longitudinal direction.

As another example, when the cross section of the glass fiber cut in the direction perpendicular to the longitudinal direction is rectangular, the shortest side is 5 to 15 탆, or 7 to 11 탆, or the shortest diameter is 5 to 15 탆 when it is elliptical, or 7 to 10 [micro] m.

The filler is included, for example, in the range of 35 to 40 weight percent of the alloy composition, and within this range the filler that is required in the alloy composition can be optimized.

The polyamide alloy high heat-resistant resin composition may further contain, for example, 1 to 3% by weight or 1 to 2% by weight of a compatibilizing agent in 100% by weight of the alloy composition. Within this range, The mechanical properties can be further improved while reducing the amount of the compatibilizing agent used.

The compatibilizer is, for example, one having a structure in which polyfunctional groups for polyamide bonding and polyphenylene oxide are grafted.

The additional functional group for the polyamide bond may be one derived from at least one compound selected from the group consisting of maleic anhydride and fumaric acid.

If necessary, the above-mentioned alloy composition may be used in combination with a flame retardant, a light stabilizer, a chain extender, a catalyst, a releasing agent, a pigment, a dye, an antistatic agent, an antimicrobial agent, a processing aid, a metal deactivator, And may further comprise at least one selected additive. The additive may be used within a range that does not adversely affect the physical properties of the polyamide alloy heat-resistant resin composition of the present invention.

The polyamide alloy high heat-resistant resin composition of the present invention is optionally mixed with the above-mentioned additives in a mixer or a super mixer and then mixed with a twin-screw extruder, a single-screw extruder, a roll- kneaded in a temperature range of 200 to 300 DEG C or 280 to 300 DEG C by using one of various mixing and processing machines such as a kneader, a kneader or a banbury mixer, and then extruded to form a pellet, And the pellets are sufficiently dried using a dehumidifying dryer or a hot-air dryer, and then injection-processed to mass-produce the polyamide alloy heat-resistant resin.

According to the present invention, it is possible to provide an electric / electronic part which is molded with the above-mentioned polyamide alloy high heat-resistant resin composition and meets the mechanical properties required for use in electrical and electronic parts such as thermal property, tensile property, bending property and impact strength . For example, an electric and electronic part having a heat distortion temperature (HDT) of 244 to 253 DEG C can be provided.

The electric / electronic component may be, for example, an injection-molded heat-resistant electric / electronic component, and may be, for example, a circuit breaker, a switch or a connector.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention, but the present invention is not limited thereto.

[ Example ]

Example  1 to 4, Comparative Example  One

The ingredients shown in the following Table 1 were put into a super mixer in the stated amounts and mixed with the lubricant and the antioxidant, and then the mixture was extruded using a twin-screw extruder at a barrel temperature of 280 to 300 DEG C And then extruded (using a pelletizer) to obtain pellets. The pellets were dried at 120 ° C for 4 hours or more, injection molded, and left to stand at room temperature for 1 day. The specimens were used as test specimens.

For reference, the materials used in Examples and Comparative Examples are as follows:

(A-1) Syndiotactic polystyrene

A molecular weight of 150,000 to 200,000 g / mol, and a melt index of 5 to 15 g / 10 min at 300 DEG C / 1.2 kg according to ASTM D1238.

(B-1) Polyamide

A resin having a relative viscosity of 2.3 to 2.5 was used in a 96% sulfuric acid solvent.

(C-1) Impact modifier

Maleic anhydride and grafted styrene-based rubber were used. The content was in the range of 1 to 5 wt%.

(C-2) Impact modifier

Glycidyl methacrylate and grafted styrene rubber were used. The content was in the range of 1 to 5 wt%.

(D-1) Glass fiber

Glass fiber surface-treated with an amino silane compound having a diameter of 10 탆 and a length of 4 mm was used.

(D-2) Glass fiber

Glass fiber surface-treated with an aminosilane compound having a diameter of 13 탆 and a length of 4 mm was used.

Category (% by weight) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 A-1 17.91 19.11 19.11 18.81 17.91 B-1 41.85 44.67 44.67 43.97 41.85 C-1 5.03 1.01 2.01 5.03 C-2 1.01 D-1 35.21 35.21 35.21 35.21 D-2 35.21

[ Test Example ]

The properties of the specimens made of the polyamide alloy high heat-resistant resin composition prepared in Examples 1 to 4 and Comparative Example 1 were measured by the following methods, and the results are shown in Table 2 below.

Appearance: The gas mark on the surface was visually observed. In Table 5, the gas mark is clear on the surface of the specimen without any gas marks. The lower the numerical value, the worse the gas mark becomes, and the numerical value 1 means that the gas marks are visible throughout the specimen appearance.

* Tensile Strength (MPa) and Tensile Report (%): measured according to ASTM D638.

Flexural Strength (MPa) and Flexural Modulus (MPa): Measured based on ASTM D790.

* Izod impact strength (specimen thickness 3.2 mm, J / m): measured at 23 ° C based on ASTM D256.

* HDT (heat distortion temperature, 18.6 kgf / C): measured according to ASTM D648.

Spiral (cm): The distance of resin movement was measured when a certain holding pressure was applied to the injection mold which had been made to a thickness of 1 mm.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 The tensile strength 131 147 128 141 107 Tensile elongation 2.6 2.7 1.9 2.7 1.7 Flexural strength 213 223 229 246 179 Flexural modulus 9967 10087 11118 9774 9458 Impact strength 134 129 108 131 97 Heat distortion temperature 247 253 249 244 245 Spiral 40.2 37.9 38.0 38.3 40.2

As shown in Table 2, Examples 1 to 4 made of the polyamide alloy high heat-resistant resin composition according to the present invention had tensile strength, tensile elongation, flexural strength Strength, flexural modulus, impact strength, and the like.

Additional Embodiment  1 to 5, Comparative Example  One

The same experiment as in Example 1 was repeated except that the component and the content shown in the following Table 3 were replaced with the component (E) and the compatibilizing agent was added.

For reference, the following materials were further used:

(A-2) Syndiotactic polystyrene

A resin having a molecular weight of 130,000 to 150,000 g / mol and a melt index of 15 to 30 g / 10 min at 300 DEG C / 1.2 kg according to ASTM D1238 was used.

(B-2) Polyamide

A resin having a relative viscosity of 2.5 to 2.8 was used in a 96% sulfuric acid solvent.

(E) compatibilizer

Fumaric acid and grafted polyphenylene oxide were used as compatibilizers. The content was in the range of 1 to 5 wt%.

division
(weight%) Additional Embodiment Additional comparison example One 2 3 4 5 One A-1 18.81 18.51 18.51 17.00 16.39 A-2 17.00 B-1 43.97 43.26 43.26 39.74 38.33 B-2 39.74 C-1 1.01 1.01 5.03 C-2 1.01 1.01 1.01 D-1 35.20 35.21 35.21 40.24 40.24 D-2 35.21 E 1.01 2.01 2.01 2.01 2.01 5.04

Category (% by weight) Additional Embodiment Additional comparison example One 2 3 4 5 One The tensile strength 181 179 184 185 189 121 Tensile elongation 2.6 2.8 2.8 2.2 2.3 1.7 Flexural strength 193 248 270 282 292 162 Flexural modulus 9313 9742 10919 11818 11706 9577 Impact strength 106 115 119 123 124 57 Heat distortion temperature 250 248 245 249 249 227 Spiral 36.8 37.1 37.2 34.2 38.6 41.3

As shown in Table 4, the additional Examples 1 to 5 made of the polyamide alloy high heat-resistant resin composition containing the compatibilizer (E) according to the present invention also include a compatibilizer (E) Further Comparative Example 1 using the glass fiber having a glass transition temperature of 200 ° C or more showed an improved effect on overall mechanical properties such as tensile strength, tensile elongation, flexural strength and impact strength, and improved thermal deformation temperature and spiral thermal properties.

As a result, according to the present invention, by incorporating the compatibilizing agent (C-1, C-2) serving as both the impact modifier in relation to the polyamide alloy high heat-resistant resin composition for electric and electronic parts having flame retardancy and appearance, C-1, C-2, and C-4, the mechanical and electrical properties of the electrical and electronic parts manufactured by using the compatibilizer (E) 2) can be somewhat reduced, but significantly improved thermal characteristics can be secured.

Claims (10)

Filler filled polyamide and syndiotactic polystyrene,
The polyamide is included in the range of 39 to 45 wt% of 100 wt% of the alloy composition,
The syndiotactic polystyrene has a weight average molecular weight (Mw) of 130,000 to 200,000 g / mol and a melt index (300 DEG C, 1.2 kg) of 5-30 g / 10 min. % ≪ / RTI > by weight,
The compatibilizing agent for both the polyamide bonding functional group and the styrene-based rubber in the form of graft structure is used in an amount of 0.5 to 7% by weight based on 100% by weight of the alloy composition,
The functional group for polyamide bonding is a functional group derived from a glycidyl (meth) acrylate compound,
A compatibilizer having a structure in which the polyfunctional group for polyamide bonding and polyphenylene oxide are grafted is contained in an amount of 1 to 3 wt% of 100 wt% of the alloy composition,
Wherein the filler is a glass fiber having an aspect ratio of not less than 0.31
Polyamide alloy heat resistant resin composition. The method according to claim 1,
The styrene-based rubber is at least one of styrene-butylene-styrene rubber, styrene-isoprene-styrene rubber, styrene-ethylene-propylene-styrene rubber, and styrene- Characterized in that it is directly bonded to the syndiotactic polystyrene resin
Polyamide alloy heat resistant resin composition. The method according to claim 1,
Wherein the polyamide has a relative viscosity of 2.3 to 2.8 as measured in a 96% sulfuric acid solvent
Polyamide alloy heat resistant resin composition. The method according to claim 1,
Wherein the filler is a glass fiber having an aspect ratio (L / D) of from 0.31 or more to less than 5
Polyamide alloy heat resistant resin composition. 5. The method of claim 4,
Wherein the glass fiber is surface-treated with aminosilane and has a length of 1 to 5 mm. The method according to claim 1,
Wherein the additional functional group for polyamide linkage is derived from at least one compound selected from maleic anhydride and fumaric acid
Polyamide alloy heat resistant resin composition. The method according to claim 1,
The composition may contain at least one additive selected from a flame retardant, a light stabilizer, a chain extender, a catalyst, a releasing agent, a pigment, a dye, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a fluorine-based antistatic agent, an inorganic filler, Characterized by comprising
Polyamide alloy heat resistant resin composition. The method according to claim 1,
Wherein the polyamide is contained in a range of 39 to 45 wt% of 100 wt% of the alloy composition, the syndiotactic polystyrene is contained in a range of 17 to 24.5 wt% of 100 wt% of the alloy composition, And styrene-based rubber in a grafted structure are included in an amount of 0.5 to 7% by weight based on 100% by weight of the alloy composition, wherein the polyfunctional group for polyamide bonding and the polyphenylene oxide are grafted Is contained in the range of 1 to 3 weight% of 100 weight% of the alloy composition, and the filler is contained in the range of 35 to 40 weight% of 100 weight% of the alloy composition.
Polyamide alloy heat resistant resin composition. A thermoplastic resin composition molded from the polyamide alloy high heat-resistant resin composition according to any one of claims 1 to 8 and having a heat distortion temperature (HDT) of 244 to 253 DEG C,
Electric and electronic parts. 10. The method of claim 9,
Wherein the electric / electronic part is a circuit breaker, a switch, or a connector
Electric and electronic parts.